Uv absorbing hydroxyphenyl benzotriazoles

ABSTRACT

LIGHT-STABILIZERS FOR POLYMERIC LIGHT-SENSITIVE PRODUCTS AND MATERIALS ARE PROVIDED WHICH PERTAIN TO THE CLASS OF 2-(2&#39;&#39;-HYDROXYPHENYL)-BENZOTRIAZOLES, COMPOSITIONS OF THE COMPOUNDS AND THE LIGHT-SENSITIVE MATERIALS ARE ALSO PROVIDED. IN FURTHER ASPECTS OF THE INVENTION LIGHT-STABLE POLY ADDITION COMPOUNDS ARE PROVIDED WHICH CONTAIN THE 2-(2&#39;&#39;HYDROXYPHENYL)-BENZOTRIAZOLE COMPOUNDS AS AN INTEGRAL PART OF THE POLY ADDITION COMPOUNDS. LIGHT-STABLE LINEAR POLYCARBONAMIDES AND LIGHT-STABLE HIGH MOLECULAR WEIGHT POLYESTER MATERIALS ARE ALSO PROVIDED.

United States Patent Oflice Int. Cl. C07d 55/04 US. Cl. 260-308 B 7Claims ABSTRACT OF THE DISCLOSURE Light-stabilizers for polymericlight-sensitive products and materials are provided which pertain to theclass of 2-(2' hydroxyphenyl)-benzotriazoles. Compositions of thecompounds and the light-sensitive materials are also provided. Infurther aspects of the invention light-stable poly addition compoundsare provided which contain the 2-(2-l1ydroxyphenyl)-benzotriazolecompounds as an in tegral part of the poly addition compounds.Light-stable linear polycarbonamides and light-stable high molecularweight polyester materials are also provided.

This application is a continuation of application Ser. No. 544,834,filed Apr. 25, 1966, which application is in turn a continuation-in-partof applications Ser. Nos. 202,664; 202,665; 202,666; 202,667 and202,668, all filed June 15, 1962, Ser. No. 328,480, filed Dec. 6, 1963and Ser. No. 535,740, filed Mar. 21, 1966, all of said priorapplications now being abandoned.

The present invention encompasses in its first five aspects newsubstituted 2-(2'-hydroxyphenyl)-benzotriazoles, compositions containingsubstituted 2-(2'-hydroxyphenyD-benzotriazoles as well as processes forpreparing said compositions.

Light-stabilizers for polymeric light-sensitive products and materialshave been known for some time, which pertain to the class of2-(2'-hydroxyphenyl)benzotriazoles. The compounds are distinguished fromother light-stabilizing agents by possessing in their absorptionspectrum maxima in the ultraviolet region, the peak of one of which isusually around 300 millimicrons, which range is referred to hereinafteras the short wavelength range, while the other peak is usually atwavelengths above 320 millimicrons, the range of which is referred tohereinafter as the long wavelength range.

It has been found that certain substituted2-(2-hydroxyphenyl)-benzotriazole compounds are valuable ultravioletlight (UV) absorbers and accordingly can be used for the protection oflight-sensitive organic materials.

The compositions according to the first through fifth aspects of theinvention comprise physical mixtures of the substituted benzotriazolecompounds and light-sensitive organic material. Thus the components ofthe compositions must be so chosen as to assure formation of a merephysical mixture. 'In other words, benzotriazole compounds having anethylenically unsaturated group must not be admixed with ethylenicallyunsaturated mono mers prior to polymerization. Furthermore,benzotriazole compounds containing a carboxyl group or an alcoholichydroxyl group or a non-aromatic amino group or equivalently reactingderivatives thereof should neither be admixed with condensation monomersprior to polycondensation, nor should they be admixed with preformed3,766,205 Patented Oct. 16, 1973 polymers under conditions which wouldcause the chemical introduction of said benzotriazole compounds into thepolymeric chain.

All of the new substituted 2-(2'-hydroxyphenyl)-benzotriazoles accordingto the invention are valuable UV absorbers. Moreover, those containing afl-mercapto propionyl moiety have been found to possess antioxidantproperties.

The substituted 2-(2'-hydroxyphenyl)-benzotriazole compounds embraced inthe teachings of this invention comprise a ring structure which can berepresented by the following fundamental formula 4 N no N-l' B I 6 5! 2(2 HYDROXYPHENYL) BENZOTRIAZOLES HAVING AN EXTERNAL CARBOXYLIC FUNC-TIONAL GROUP The first invention aspect concerns new substituted2-(2-hydroxyphenyl)-benzotriazole compounds, useful for the protectionof light-sensitive organic materials, i.e. of high polymeric materials,by physically admixing them with the said light-sensitive materials, andfor the production of UV filters.

According to this aspect of the invention, it has been found thatvaluable light stabilizers are obtained if an azo dyestuff of theformula R represents hydrogen, an alkyl, aralkyl or an acyl group,

and Q represents the nitro group or the primary amino group,

is (i) reduced when said Q is the nitro group or is oxidized when said Qis the primary amino group, and (ii) the hydroxyl group in the 2position is liberated if esterified or etherified to form a triazolecompound of the In these formulas X represents a divalent bridging groupwherein Z is hydrogen or an alkyl, preferably lower alkyl group and theX moiety is bound to the nucleus A and/or B by way of O, S or C, tonucleus B, preferably by way of O;

Y represents a divalet aliphatic, cycloaliphatic, monocyclic araliphaticor monocyclic aromatic radical, whereby hetero atoms possibly containedin said radicals are separated by at least two carbon atoms from oneanother or from hetero atoms contained in Y and W;

W represents the CN-, a CONRR"- or a COOR group in which R, R' or R" areindependently hydrogen, an alkyl, cycloalkyl, monocyclic aralkyl ormonocyclic aryl radical;

in and 11 each independently represent 1 or 2;

and wherein nucleus A is a monocyclic arylene radical, if desiredsubstituted in positions 4, and 6 by preferably at most two of thefollowing substituents, alkyl, alkoxy, carboxy, carboxylic acid ester,carboxylic acid amide, sulphonic acid amide, alkyl sulphonyl groups orhalogen;

nucleus B is a monocyclic arylene radical which besides the hydroxygroup in the 2' position is possibly substituted in preferably at mosttwo of the positions 3', 4 and 5' by hydrocarbon groups and alkoxygroups and wherein the grouping (X) Y--W] is bound to at least one ofthe said positions 4, 5, 6, 3, 4, or 5'.

If benzene ring A is substituted it can contain, for example, halogenssuch as fluorine, chlorine or bromine, also alkyl groups such as methyl,ethyl, n-propyl, isopropyl, n-, isoor tert. butyl groups, alkoxy groupssuch as methoxy or butoxy groups, carboxylic acid groups, carboxylicacid ester groups, i.e. carboxylic acid alkylester groups such ascarbomethoxy, carboethoxy, carbopropoxy or carbobutoxy groups,carboxylic acid or sulphonic acid amide groups possible aliphatically,cycloaliphatically, araliphatically, or aromatically substituted at thenitrogen atom such as carboxylic acid or sulphonic acid amide,methylamide, ethylamide, cyclohexylamide, benzylamide, phenylamide,dimethylamide, diethylamide, N-methyl-N- cyclohexylamide,'y-methoxypropylamide, piperidide or morpholide groups, as well asalkylsulphonyl groups such as methyl or ethyl sulfonyl groups. If thebenzene ring B is substituted it can contain open chain or cyclichydrocarbon groups such as methyl, ethyl, benzyl, cyclohexyl or phenylgroups, alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy orn-butoxy groups, or halogens such as chlorine or bromine.

If the moiety {(X) Y-W] is attached to nucleus A then it is linkedpreferably to the 5-position. If it is linked to the 3-position ofnucleus B it is important that the moiety does not form spontaneously at5 or 6 mem bered lactone ring with the hydroxyl group in the 2'position. This would exclude such moieties as the CH COOH or CH CH COOHgroups, in said 3' position.

Benztriazole compounds which absorb particularly at long wave lengthsare obtained if the starting materials are so chosen that, in the endproducts, acidifying sub stituents are present in the 4- and/orS-position and basifying substituents are present in the 3' and/or5'-position. Benztriazole compounds having particularly high molarextinction in the range of 330-350 m are obtained if there are basifyingsubstituents in the 5- and/ or 4-position. The molar absorption in theregion of 300 m is promoted by possibly further substituted alkylsubstituents in the 3'-position.

Examples of basifying substituents are alkoxy groups such as themethoxy, isopropoxy, cyclohexyloxy and benzyloxy groups; examples ofacidifying substituents are alkylsulphonyl groups such as the methyl andethyl sulphonyl groups, sulphonic acid amide groups such as thesulphonic acid methyl, butyl and cyclohexyl amide groups as well as thecarboxyl groups and its esters or amides.

If Y is a divalent aliphatic radical it is preferably an alkyleneradical such as the methylene, 1,1- or 1,2-ethylene, 1,1-, 1,2- or1,3-propylene, 1,1-, 1,2-, 1,3-, 1,4- or 2,3-butylene radical, and alsoan alkylene radical interrupted by hetero atoms such as, e.g. theB,;8'-diethylene ether radical. If it is an araliphatic radical then itis, e.g. a benzylene radical C H CH or a phenethylene radical C H CH CHIf Y is an aromatic radical thenit is mainly an arylene radical of thebenzene series, e.g. the 1,2-, 1,3- or 1,4- phenylene radical.

Among the compounds of Formula II the ones are preferred in which Ystands for an alkylene group with 1-4 carbon atoms such as themethylene, 1,2-ethylene or 1,4-butylene group, a phenylene group such asthe 1,2 or 1,4 phenylene group, an aralkylene group such as the(1,2-benzylene group or an alkylene group including a sulphur atom andcontaining 4 to 6 carbon atoms such as the When R, R and R" are each analiphatic radical then they are, e.g. an alkyl radical, for example thee hy ethyl, propyl, isopropyl, n-, sec. or tert. butyl-, amyl-, hexyl-,octyl-, decyl-, dodecyl-, tetradecyl-, hexadecylor octadecyl-radical. Ifthey are a cycloaliphatic radical then they are, e.g. a cyclohexylradical, and when they are an araliphatic radical, this is, e.g. thebenzyl radical. Examples of aromatic radicals symbolised by R or R" arethe phenyl or the 2-, 3- or 4-methylphenyl or 2-, 3-, or 4-chlorophenylradicals.

The azobenzene compounds usable as starting materials of Formula Iwherein Q is the nitro group are obtained, for example, by coupling ano-nitrobenzene diazonium compound with a B-unsubstituted phenol couplingin the 2-position to the hydroxyl group, the components being so chosenthat the azobenzene compound formed contains the group {-(X) YW] atleast once.

The ring of the o-nitroazobenzene compound is closed to form thetriazole of Formula II by the usual methods, e.g. witth zinc dust in analkaline medium.

Starting materials of Formula I wherein Q is the primary amino group areobtained, for example, by coupling a 2-hydroxy-, 2-alkoxyor2-acyloxybenzene diazonium compound with an aminobenzene coupling in the2-position to the amino group, the components in this case too being sochosen that the azobenzene compound formed contains the group {(X),, YW]at least once, and then, if necessary, dealkylating the alkoxy group orsaponifying the acyloxy group.

The o-aminobenzene compound is oxidised to form the triazole of theFormula II by the usual methods, for example with Cu-(II)-salts inaqueous/alkaline medium.

Ether groups are dealkylated preferably with hydrogen bromide in glacialacetic acid, and acyloxy groups are hydrolised in aqueous/acid oraqueous/alkaline medium.

A modification of the process for the production of 2-(2'-hydroxyphenyl)-benztriazole compounds which possibly containesterified carboxyl groups in an alkoxy and/or in an alkylthio radicalconsists in reacting a 6'-unsubstituted2-(2'-hydroxyphenyl)-benztriazole compound containing at least one otherhydroxyl group in the nucleus which can be etherified and/or at leastone mercapto group which can be etherified, with an organic compoundcontaining possibly esterified carboxyl groups and mobile halogen, forexample, with chloroacetic acid or fi-carboethoxy-propionyl chloride.

The reaction is performed by the usual methods, for example by heatingin an organic solvent, possibly in the presence of an agent which splitsoff acid, e.g. an alkali metal salt of a low fatty acid such as sodiumacetate.

Another modification of the process for the production of2-(2-hydroxyphenyl)-benztriazole compounds containing possiblyesterified carboxyl groups in an alkoxy and/ or alkylthio radical,consists in adding to a 6-unsub stituted '2 (2hydroxyphenyD-benztriazole compound containing at least one otherreactive hydroxyl group in the nucleus and/or at least an etherifiablemercapto group, a reactive organic compound which contains possiblyesterified carboxyl groups or which, on the addition, liberates suchgroups, for example acrylonitrile and succinic acid anhydride, thelatter being useful for reaction with hydroxyl groups only.

The addition is performed by the usual methods such as heating the tworeaction components, advantageously in an organic solvent, possibly inthe presence of polymerisation inhibitors, e.g. methylene blue or2,6-di-tert-butyl-4- methylphenol.

A further modification of the process consists in reacting a2-(2'-hydroxyphenyl)-benztriazole compound having a substituentcontaining mobile halogen such as, e.g. the carboxylic acid or sulphonicacid chloride group, with a compound containing a condensable group suchas, e.g. amino or hydroxyl group, which compound also contains at leastone possibly modified carboxyl group. Examples of such condensablecompounds are amino and hydroxy carboxylic acids as well as derivativesthereof such as glycine, ,B-hydroxypropionitrile, glycolic acid ethylester and p-aminobenzoic acid isopropylamide.

The condensation is performed by the usual methods, e.g. by heating thetwo components in the presence of acid binding agents such as tertiarynitrogen bases and in the presence of salts of weak acids, e.g.pyridine, sodium carbonate, calcium carbonate or potassium acetate,possibly in an organic solvent such as acetone or chlorobenzene.

Another modification of the process consists in adding to a2(2'-hydroxyphenyl)-benztriazole compound having a substituentcontaining at least one group capable of addition, a compound containingmobile hydrogen which compound also contains at least one possiblymodified carboxyl group. Examples of such groups capable of addition arein particular vinyl or vinylene groups activated by vicinal acidifyinggroup such as the sulphonyl, carbonyl or nitrile group such as theacryloyl group but also heterocyclic esters or amides such as lactonesor lactams, e.g. the fl-propiolactone group and cyclic anhydrides suchas the succinic acid anhydride group. Examples of carboxylated compoundscontaining mobile hydrogen in the form of hy droxyl mercapto and aminogroups are aminocarboxylic acids, hydroxycarboxylic acids and mercaptocarbonic acids and derivatives thereof having a modified carboxyl groupsuch as fi-thiopropionic acid, alanine ethyl ester andfi-hydroxypropionitrile. Also suitable for addition to vinyl andvinylide groups are sulphinic acids containing carboxyl groups andhydrocyanic acid.

The addition is performed by the usual methods, for example by heatingthe two components in organic solvents such as chlorobenzene, ethyleneglycol dimethyl ether, possibly in the presence of catalysts, e.g. acidssuch as sulphuric acid, H-form of ion exchangers and hydrofiuoroboricacid in the case of lactones or basic catalysts such as triethylamine orsodium tert. butylate in the case of activated ethylenes, or catalystsyielding free radicals, such as benzoylperoxide, which are used tocatalize the addition of mercaptans containing carboxyl groups toolefins.

The carboxyl, carboxylic acid ester, carboxylic acid amide and nitrilegroups contained in compounds of Formulae I and II, symbolised by W, canbe converted into each other by reactions known per se. Thus, forexample, carboxyl groups are esterified, possibly by way of theirhalide, with alcohol or alkali alcoholates, carboxylic acid halide orcarboxylic acid ester groups are amided with primary or secondary aminesor nitrile groups are esterified by way of their iminoether groups withalkali alcoholates. Carboxylic acid ester groups of higher alcohols areintroduced advantageously by such as subsequent modification of thecarboxyl or nitrile group or ester groups of lower alkanols.

Depending on their substitution, the new substituted 2-(2'-hydroxyphenyl)-benztriazole compounds of Formula II are colourlessto pale yellowish coloured. Those which absorb the greatest amount of UVlight are particularly valuable. Compared with previously knowncompounds of similar constitution they have improved properties fortechnical application such as, e.g. solubility, range of action andimproved fastness to sublimation. They are incorporated intolight-sensitive carriers in amounts of 0.0015%, in particular in amountsof 0.01-1%, calculated on the carrier.

Free carbonic acids are useful, especially in form of their salts withaliphatic amines such as diethanolamine or triethanolamine for thestabilization of aqueous or alcoholic solutions of light-sensitivematerials such as cosmetic products. Carboxylic acid esters especiallythe one of higher alkanols such as the octyl and dodecyl esters areuseful for the stabilization of unpolar polymers such as polyethyleneand polypropylene. Nitriles, carboxylic acid amides ars well as estersof lower alkanols are useful for the stabilization of carriers ofintermediate polarity. More particularly, compounds of the formula themloecular weight of which compounds does not exceed 600, and in theformula of which (III) X is a member selected from the group consistingof lower alkyl 0 lower alkyl W is a member selected from the groupconsisting of --COO.alkyl wherein the alkyl moiety is alkyl of l to 18carbon atoms, -COO.cycloalkyl wherein the cycloalkyl moiety iscycloalkyl of 4 to 12 carbon atoms, -COO-benzyl, -COO-phenyl, -CN and Rbeing selected from among hydrogen and lower alkyl,

and

R" being selected from among alkyl of from 1 to 18 carbon atoms,cyclohexyl, benzyl and lower alkenyl, or R and R" taken together withthe nitrogen atom to which they are linked, represent morpholino,

m and n are each independently of the other, one of the integers 1 and2,

the first {(X) Y-W] grouping being linked in one of the positions 5 atring A, or 3', 4' or 5' at ring B, and a second grouping {(X) YW], ifpresent, being linked to one of the aforesaid positions at that ring, ofrings A and B, which is free from said first grouping,

nucleus A is substituted in at least one of the 4, 5 and 6 positionswhich is free from said grouping by at least one member selected fromthe group consisting of hydrogen, lower alkyl, lower alkoxy,alkoxycarbonyl of from 2 to 19 carbon atoms, cyclohexyloxycarbonyl,benzyloxycarbonyl, phenoxycarbonyl, N-alkyl-substituted carbamyl andN-alkyl-substituted sulfamyl, each alkyl in the last two members havingfrom 1 to 18 carbon atoms, and the total of carbon atoms in alkylsubstituents of each of said members not exceeding 20,N-cycloheXyl-sulfamyl, N-benzylsulfamyl, N-lower alkoxy-loweralkyl-sulfamyl, N-hydroXy-lowcr alkyl-sulfamyl, lower alkyl-sulfonyl andhalogen,

and the nucleus B is substituted in at least one of the 3'-, 4- and5'-positions, not substituted by said grouping {(X) YW], by a memberselected from the group consisting of hydrogen, lower alkyl, cycloalkylof from 5 to 6 ring carbon atoms, chlorine, benzyl or phenyl,

are useful as UV-absorbers particularly in polymers of low to mediumpolarity, such as cellulose acetate, polymethylmethacrylate, polystyreneand related polymers. In contrast to known benzotriazole derivativesused as UV-absorbers, the novel compounds of Formula III are especiallyvaluable due to their good compatibility with the last-mentionedpolymeric materials, which allows the build up of thin and neverthelessUV-dense structures.

Among the compounds falling under Formula III,

those of the formula N x)n-1-Yw:| 5 I 2' a m A N- B 6 the molecularweight of which compounds does not exceed 600, and in the formula ofwhich X is a member selected from the group consisting of wherein said Xis bound only by one of the oxygen, carbon and sulfur atoms contained insaid X to at most one of the nuclei A and B,

Y has the same meaning as in Formula III, W is a member selected fromthe group consisting of -COO.alkyl wherein the alkyl moiety is alkyl of4 to 18 carbon atoms, -COO.cycloalkyl wherein the cyclo alkyl moiety iscycloalkyl of 4 to 12 carbon atoms and COO-benzyl,

m and n are each independently of the other, one of the integers l and2,

the first and second groupings {(X) YW] being linked to rings A and B,respectively, in the same manner as in the compounds of Formula III,

nucleus A is substituted in at least one of the 4, 5 and 6 positionswhich is free from said grouping 8 lower alkyl-sulfamyl, N-hydroxy-loweralkyl-sulfamyl,

lower alkyl-sulfonyl and halogen, and the nuceus B is substituted in thesame manner as in compounds of Formula III,

are useful as UV-absorbers particularly in poly-a-olefines such aspolyethylene and polypropylene materials, be it as plates, sheets, foilsor fiber materials.

A further subclass of compounds falling under Formula II are compoundsof the formula wherein X represents a member selected from the groupconsisting of -CO and AD each of R and R represents hydrogen, loweralkyl, hydroxy-lower alkyl or lower alkoxy-lower alkyl, or R and R takentogether with the nitrogen atom to which they are linked representmorpholino,

Y represents lower alkylene attached to the 5-position of ring B, orbutylene or benzylene attached to the 3'- position of ring B,

and ring B is further substituted, apart from the grouping -Y'COOH, by amember selected from the group consisting of hydrogen and lower alkyl,

which compounds as well as their salts which are soluble orhomogeneously distributable in aqueous or alcoholic media, are usefulparticularly as UV-absorbers in alcoholic or aqueous solutions, lotionsand dispersions required in the cosmetic industry.

Finally, compounds of the formula N Ht wherein Y" represents loweralkylene,

and ring B is further substituted by hydrogen or lower alkyl, preferablyin the form of their soluble salts, have usefulness in the same manneras the compounds of Formula V and the above-defined salts of the lattercompounds.

The principal carriers for the new compounds of Formula II are polymers,chiefly completely synthetic polymers e.g. addition polymers, inparticular polymers of ethylenically unsaturated monomers such as, e.g.polyvinyl chloride, polyvinylidene chloride, styrene polymers, dienepolymers as well as their copolymers, polyethylene, polypropylene,polyacryl compounds, in particular polymethylmethacrylate orpolyacrylonitrile, also condensation polymers such as polyesters, e.g.polyethylene glycol terephthalates, or polyamides e.g. polycaprolactam,or also mixed polymers such as, e.g. polyester resins i.e. additioncopolymers of unsaturated polyesters with ethylenically unsaturatedmonomers such as styrene and methylmethacrylate, also natural polymersor synthetic modifications thereof such as, e.g. cellulose, celluloseesters and ethers and proteins.

The molecular weight of the polymers mentioned above plays a subsidiarypart as long as it remains within the margins necessary for thecharacteristic mechanical properties of the polymers concerned.Depending on the polymer, it can be between 1000 and several millions.The new substituted 2-(2-hydroxyphenyl)-benztriazole compounds areincorporated into these polymers depending on the type of polymere.g. byworking in at least one of these compounds and possibly other additivessuch as, e.g. plasticisers, antioxidants, heat stabilisers and pigments,into the melts by the methods usual in the industry before or duringmoulding, or by dissolving them in the corresponding monomers beforepolymerisation provided they do not take part in the polymerisation, orby dissolving the polymers and the additives in solvents andsubsequently evaporating off the latter. The new substituted2-(2'-hydroxyphenyl)-benztriazole compounds I can also be drawn frombaths, e.g. from aqueous dispersions, onto films or threads, or can beadded directly to the liquid containing dissolved therein the substratesto be protected in form of their neutral solution in water or alcohols.

As the compositions according to the invention comprise only physicalmixtures of the substituted benztriazole compounds and thelight-sensitive organic material benztriazole compounds containing acarboxy group or an equivalently reacting derivative thereof should notbe admixed with condensation monomers prior to polycondensation norshould they be admixed with performed polycondensates under conditionswhich would cause the chemical introduction of said benztriazolecompounds into the polymeric chain.

The light-sensitive materials can also be protected from the injuriouseffect of light by painting them with protective coating, e.g. alacquer, containing at least one compound of Formula I as defined, or bycovering them with covers-preferably film-like--containing such actinicagents. In these two cases, the amount of the actinic agents to be addedis advantageously 10-30% (calculated on the protective coatingmaterial), for coatings of less than 0.01 mm. thickness and 1-10% forprotective coatings of 0.01-0.1 mm. thickness. The more colourless theactinic agents are, the more valuable are they as they then do not lenda yellow colouring to the end products.

In non-polar polymers, those benztriazole compounds are particularlysuitable which themselves contain as few as possible polar groups suchas secondary carboxylic acid or sulphonic acid amide groupings. In thiscase, generally products having a low melting point are preferredbecause of their solubility.

In general, it is recommended that the possible use of a specificproduct to be estimated by solubility trials. For example, if theproduct is diflicultly soluble, even hot, in the solvents known for thepolymers to be protected, then unfavourable results in this polymer areto be expected.

For certain uses, particularly when warm chips of polymers are powderedwith protective substances, the products which melt at above thetemperature at which the polymers concerned melt and, in spite of this,are sufficiently soluble in the melted polymers, are particularlyvaluable.

Especially valuable light stabilizers according to the invention, due totheir case of preparation as well as to their solubility in non-polarsolvents and carriers are those in which in equals 1, n equals 1, Y isan alkylene group of 1 to 4 carbon atoms or an aralkylene group of 7 to8 carbon atoms. As an aralkylene group are especially good. W is a--COOE wherein E is alkyl, cycloalkyl or benzyl wherein the alkylcontains preferably 4 to 12 carbon atoms and the cycloalkyl contains to7 carbon atoms. The nucleus A is substituted at all the 4-, 5- and6-positions by hydrogen or at the 4- and 6-positions by hydrogen and atthe 5-position by chlorine, methyl, methoxy or --COOE' in which E mustbe the same radical as is found for E (in other words when A issubstituted by -COOE, the resulting compound is a diester derived from adicarboxylic acid in which both carboxyl groups are esterified with thesame alcohol. In said diesters the alkyl groups represented by E containpreferably one to 8 carbon atoms). The nucleus B is substituted in the3-, 4'- or 5'-positions, preferably at the 3- or 5'-position by --Y--Wand in the remaining of said positions by hydrogen or hydrogen andmethyl or hydrogen and chlorine.

The light sensitive carriers can cover a wide range of organicmaterials. Cosmetic products containing fats, oils and/or fatty acidorganic soaps especially soaps of long chain unsaturated acids, areuseable. Especially suitable are cellulose esters, addition polymers ofethylenically unsaturated monomers, e.g. polyethylene, polypropylene,polyvinylchloride, polymethylmethacrylate, copolymers of unsaturatedpolymeric condensates and ethylenically unsaturated monomers. Howeverthe carrier is by no means intended to be limited to these latterpolymeric materials as is evidenced in the specification, previouslymentioned.

The following examples illustrate the invention. Where not otherwisestated, parts are given therein as parts by weight. The temperatures arein degrees centigrade. The relationship of parts by weight to parts byvolume is as that of kilogrammes to litres.

EXAMPLE 1 The still moist azo dyestuff obtained by coupling 26.1 partsof diazotised 3-nitro-4-aminobenzene sulphonic acid-,B-hydroxyethylamide and 18.0 parts of B-(3-methyl-4-hydroxyphenyl)-propionic acid, is stirred with 200 parts by volume of 2N sodium hydroxide solution. (The 5-(3-methyl-4-hydroxyphenyl)-propionic acid is obtained by saponifying theaddition product of acrylonitrile and ocresol.) 30 parts of zinc dustare added to the solution obtained and then 50 parts by volume ofconcentrated sodium hydroxide solution are added dropwise within 1 hour,the temperature being kept under 45. The solution, which is now yellow,is acidified with concentrated hydrochloric acid while cooling untilCongo red paper is turned slightly blue. The precipitate which forms isfiltered off under suction, washed well with water, then stirred withdilute sodium carbonate solution and filtered. On acidifying thefiltrate, 2-(2'-hydroxy-3-methyl-5'-B- carboxyethylphenyl)-benztriazoleS-sulphonic acid-B-hydroxyethylamide is obtained.

Form methyl ethyl ketone/o-dichlorobenzene the product crystallises inpractically colourless crystals melting at 174. The yellow meltrecrystallises and melts then at 194. From dilute alcohol the formmelting at 194 crystallises directly in yellowish needles.

When repeating Example 1, but using in lieu of 18.0 parts offl-(3-methyl-4-hydroxyphenyl)-propionic acid an equivalent amount offl-(3-methyl-4-hydroxyphenyl)- propionitrile and otherwise repeating thesame procedure as in the example, the compound 2-[2'-hydroxy-3-methyl- 5(/3-cyanoethyl)phenyl]-benzotriazole-5-sulfonic acidfl-hydroxyethylamide is obtained.

When repeating Example 1, but using an equivalent amount ofo-nitraniline instead of 26.1 parts of 3-nitro-4- aminobenzene sulfonicacid fl-hydroxyethylamide, and an equivalent amount offl-(p-hydroxyphenyl)-propionitrile in lieu of 18.0 parts ofB-(3-methyl-4-hydroxyphenyl)- propionic acid, there is obtained2[2'-hydroxy-5'-(,B- cyanoethyl phenyl] -benzotriazole.

Analogous proceeding using the corresponding 4-amino-3-nitrobenzenesulphonic acid amides yields the followingcompounds:

2-(2-hydroxy-3'-methyl-5-[i-carboxyethylphenyl)-benztriazole-S-sulfonicacid butylamide 2- 2-hydroxy-3 -methyl-5 -fi-carboxyethylphenyl-benztriazole-S-sulfonic acid cyclohexylamide 2- 2'-hydroxy-3-methy1-5'-B-carboxyethylphenyl -benztriazole-S-sulfonic aciddiethylamide2-(2'-hydroxy-3'-methyl-5'-fl-carboxyethylphenyl)-benztriazole-S-sulfonicacid-'y-methoxypropylamide2-(2-hydroxy-3'-methyl-5-fi-carboxyethylphenyl)-benztriazole-S-sulfonicacid benzylamide.

EXAMPLE 2 The still moist dyestutf, obtained by coupling 13.8 parts ofdiazotised o-nitraniline and 24.2 parts of 2-hydroxy 2' carboxymethyl-l,l-diphenylmethane, is dissolved in 400 parts by volume of waterand 100 parts by volume of concentrated sodium hydroxide solution. Afterthe addition of 40 parts of zinc dust, 50 parts by volume ofconcentrated ammonia are added dropwise whereupon the colour quicklychanges from red-violet to yellow-green. The mixture is stirred foranother hour at 80 and then poured into a solution of 300 parts byvolume of concentrated hydrochloric acid in 1000 parts by volume ofwater. The precipitated 2-[2 hydroxy-3'- (o carboxyphenylmethyl) 5'methylphenyl]-benztriazole is purified by recrystallisation from glacialacetic acid/chlorobenzene. M.P. 210.

2-[2' hydroxy 3 (o-carboxyphenylmethyl) 5'- chlorophenyl]-benztriazoleis obtained in an analogous manner on using 2 hydroxy 2' carboxy 5chloro- 1,1 diphenylmethane instead of the 2-hydroxy-2-carboxy 5 methyl1,1 diphenylmethane mentioned. The diphenylmethane compounds employedare obtained by reduction from the corresponding benzophenonederivatives with zinc dust in alkaline medium.

EXAMPLE 3 The still moist azo dyestufi, obtained by coupling 55.5 partsof diazotised 3 nitro 4 aminobenzene sulphonic acid carboxymethylamide,and 21.6 parts of p-cresol is dissolved in 400 parts by volume of 2 Nsodium hydroxide solution. (The 3 nitro 4 aminobenzene sulphonic acidcarboxymethylamide is obtained by reaction of 3-nitro- 4 chlorobenzenesulphonic acid chloride with glycine in a weakly alkaline medium at roomtemperature and subsequent reaction with ammonia at 130.) 50 parts ofzinc dust are added, the temperature being kept at 35- 40. To completethe decolouration, 40 parts by volume of concentrated sodium hydroxidesolution are added and the mixture is stirred for 1 hour. The2-(2'-hydroxy-5- methylphenyl)-benztriazole 5 sulphonic acidcarboxymethylamide is precipitated by the addition of concentratedhydrochloric acid until the reaction is acid to Congo paper. It ispurified by dissolving in sodium carbonate solution, filtration, againprecipitating followed by recrystallisation from dimethylformamide/glacial acetic acid. The compound decomposes at around 250.

If instead of the 21.6 parts of p-cresol, 36 parts of ,8 (3 methyl 4hydroxyphenyl) propionic acid are used, then 2 (2'-hydroxy 3' methyl 5 3carboxyethylphenyl)-benztriazole 5 sulphonic acid carboxymethylamide isobtained.

EXAMPLE 4 parts of 2 (2 hydroxy 5' ,8 carboxyethylphenyl)-benztriazole,obtained by using ,8 p hydroxyphenyl-propionic acid and o-nitraniline asdescribed in Example 1, and 100 parts by volume of toluene, 20 parts byvolume of butanol and 0.5 part of p-toluene sulphonic acid chloride areheated in a water separator until, over a period of 3 hours, no morewater is separated. After washing with 2% sodium carbonate solution andevaporation olf the solvent, 2 (2 hydroxy-5-3-carbobutoxyethylphenyl)-benztriazole is obtained. M.P. 92.(Recrystallised from ligroin, B.P. 100-140.)

On using the corresponding alcohols, 2 (2' hydroxy- 5' p carbodecyloxyethylphenyl)-benztriazole, 2-(2'- hydroxy 5' B carbo pethylhexyloxy-ethylphenyl)- benztriazole, 2 (2 hydroxy 5 ficarbocyclohexyloxy-ethylphenyl)-benztriazole are obtained by the sameprocess.

The analogous ethyl ether is obtained by normal Fischer esterificationin ethanol.

EXAMPLE 5 28.3 parts of 2-(2-hydroxy 5' Bcarboxyethylphenyl)-benztriazole are dissolved in 300 parts by volume ofdry dimethylformamide. 14.0 parts of thionyl chloride are added dropwiseto this solution whereupon the temperature is raised to 50-60". Afterstanding for 15 minutes at this temperature, the excess thionyl chlorideis drawn off under vacuum and 20.0 parts of cyclohexylamine are added tothe resultant solution of the acid chloride in such a way that thetemperature does not rise above 30. The mixture is then slowly heated ina water bath and kept for 1 hour in a boiling water bath. After cooling,the mixture is made acid to Congo paper with dilute hydrochloric acid,the 2-(2 hydroxy-5'13- carbocyclohexylamidoethylphenyl)benztriazole isfiltered oil under under suction and recrystallised fromdimethylformamide/ glacial acetic acid. M.P. 235.

On using the corresponding amines, 2-(2-hydroxy-5'-ficarbobutylamidoethylphenyl) -benztriazole, 2-(2-hydroxy- 5'fl-carbobenzylamidoethylphenyl)-benztriazole, 2-(2'- hydroxy 5'-3-carb0allylamidoethylphenyl)-benztriazole are obtained.

The 2-(2'-hydroxy-5'-carboxyethylphenyl)-benztriazole can be obtained byreducing the monazo dyestutf obtained from diazotised o nitranilinep-hydroxyhydrocinnarnic acid.

EXAMPLE 6 The still moist azo dyestuff, obtained by coupling 26.3 partsof diazotised o-tosyloxy-aniline and 18.1 parts of3-carboxymethoxy-4-methylaniline in glacial acetic acid solution, isdissolved in parts by volume of pyridine and 100 parts by volume ofwater. A sodium hypochlorite solution (produced by introducing 17.7parts of chlorine gas into 100 parts by volume of 2.5 N ice cold sodiumhydroxide solution) is added at 20 and the whole is stirred for 24hours. 10 parts of solid sodium hydroxide are then added, the pyridineis distilled oil? and the aqueous solution is refluxed for another 2hours. On acidifying, the 2(2'-hydroxyphenyl)-5-carboxymethoxy-6-methylbenztriazole precipitatesand is filtered off under suction.

The same product is obtained if2-phenyl-2,5-dihydroxy-6-methyl-benztriazole is partially alkylated withthe sodium salt of chloroacetic acid. The former compound is obtained bycoupling diazotised o-methoxyaniline and 3-methoxy-4-methyl aniline inan alkaline solution, oxidising with copper-(II)-salts anddemethylating.

EXAMPLE 7 27.1 parts of 2 (2'-hydroxy-3,5'-dimethylphenyl)-5-mercapto-benztriazole (M.P. 128) in 300 parts by volume of dioxan arerefluxed for 4 hours in an atmosphere of nitrogen with 10 parts ofacrylic acid ethyl ester and 5 parts of triethylamine. The solvent isthen distilled oif under vacuum and the residue is crystallised fromligroin. 28 parts of2-(2'-hydroxy-3,5'-dimethylphenyl)-5-8-carboethoxyethylmercapto-benztriazoleare obtained, M.P. 87.

The 2 (2-hydroxy-3',5'-dimethylphenyl)-5-mercapto benztriazole used asstarting material is obtained from 2- (2 hydroxy3',5'-dimethylphenyl)benztriazole-S-sulphonic acid chloride by reductionwith zinc dust and hydrochloric acid in glacial acetic acid. Thissulphonic acid chloride is produced by the usual methods from thecorresponding sulphonic acid which is obtained by reduction of themonazo dyestulf produced from diazotised o-nitraniline-p-sulphonic acid2,4-dimethylphenol. If the2-(2'-hydroxy-3',5'-dimethylphenyl)-benztriazole-S-sulphonic acidchloride is reduced by means of sodium sulphite into the sulphinic acidand if the latter is reacted as described above with acrylonitrile, then2-(2'-hydroxy-3',5-dimeth- 13 ylphenyl) [i-cyanoethyl sulphonylbenztriazole is obtained.

EXAMPLE 8 22.7 parts of 2-(2',4'-dihyroxyphenyl)-benztriazole in 50parts by volume of chlorobenzene are refluxed for 3 hours with 10.0parts of succinic acid anhydride and 0.3 part of toluene sulphonic acidchloride. After cooling, the 2 (2hydroxy-4'-,8-carboxypropionyloxy-phenyl)-benztriazole is obtained. 2(2',4'-dihydroxyphenyl)benztriazole is obtained by reducing the monoazodyestulf obtained from diazotised o-nitraniline and resorcin.

EXAMPLE 9 A suspension of 28.8 parts of2-(2'-hydroxy-5-methylphenyl)-benztriazole-5-carboxylic chloride in 100parts by volume of dioxan is added dropwise at room temperature to asolution of 22.0 parts of glycine ethyl ester in 200 parts by volume ofpyridine. The mixture is stirred for 2 hours at room temperature andthen heated to 50. After cooling, the reaction mixture is poured into2000 parts by volume of ice cold 2 N hydrochloric acid and the 2(2-hydroxy-5'-methylphenyl)-benztriazole-5-carboxylic acidcarboethoxymethylamide obtained is filtered oil under suction.

Analogously 2-(2-hydroxy-5'-methylphenyl)-benztriazole-S-carboxylicacid-N-methyl-carboethoxymethylamide is obtained when the ethylester ofsarcosine is used instead of the glycine ethylester. For the preparationof 2-(2'-hydroxy-5'-methylphenyl)benzotriazole-S-carboxylic acidpcarbomethoxyphenylester the corresponding benzotriazole- S-carboxylicacid chloride is reacted with p-hydroxy benzoic acid methylester ataround 90. 2-(2-hydroxy-5- methylphenyl)-benzotriazole-S-carboxylic acidchloride is obtained by reacting the corresponding carboxylic acid withthionyl chloride. The latter is obtained by reducing the monoazodyestufi produced from diazotized 4-amino- 3-nitrobenzoic acid p-cresol.

2 (2' hydroxy-5'-methylphenyl)-5-[carbo-B-(B'-carbethoxy ethyl)mercapto-ethoxy]-benzotriazole is obtained from the correspondingbenzotriazole S-carboxylic acid chloride by condensation withfi-(E-ethoxycarbonylethyl-mercapto)-ethanol under reflux.

EXAMPLE 10 33.7 parts of2-(2'-hydroxy-3',5'-dimethylphenyl)-benzotriazole-S-sulfonic acidchloride (compare Example 7) suspended in 100 parts by volume ofchlorobenzene are slowly added at 50 to a solution of 50 parts ofphydroxy benzoic acid methyl ester in 100 parts by volume ofchloro-benzene and 12 parts of dimethyl aniline and then the mixture isheated for 2 hours on a boiling water bath. The mixture is then covered,when ice cold, with a solution of 150 parts by volume of 2 N sodiumhydroxide solution in 200 parts by volume of ethanol and, after wellshaking, the aqueous-alcoholic phase is isolated. Careful acidificationin the cold with 5 N-hydrochloric acid, produces2-(2-hydroxy-3',5'-dimethylphenyl)-benzotriazole-S-sulfonicacid-p-carbomethoxyphenyl ester.

EXAMPLE 11 36.5 parts of 2-(2-hydroxy-5'-tert.butylphenyl)-benztriazole-S-sulphonic acid chloride (producedanalogously to Example 7) suspended in 100 parts of dioxan are added atroom temperature to a solution of parts of glycine in 200 parts ofpyridine and parts of triethylamine. After standing for 4 hours at roomtemperature, the mixture is poured, while cooling, into 5000 parts byvolume of 2 N hydrochloric acid whereupon the 2-(2'-hydroxy- 5-tert.butylphenyl)-benztriazole 5 sulphonic acid-carboxymethylamideprecipitates. Recrystallised from alcohol it melts at 179.

If instead of the 2-(2'-hydroxy-5-tert. butylphenyD- benztriazole 5sulphonic acid chloride, an equivalent amount of 2- (2'-hydroxy-5'-cyclohexylpheny1 benztria- 14 zole-S-sulphonic acid chloride,2-(2'-hydroxy-S-benzylphenyl)-benztriazo1e-5-sulphonic acid chloride or2-(2- hydroxy-5-phenylphenyl) benztriazole-S-sulphonic acid chloride isused, then 2-(2-hydroxy-5-cyclohexylphenyl)- benztriazole-S-sulphonicacid-carboxymethylamide, or 2- (2'-hydroxy-5'-benzylphenyl)-benztriazole5 sulphonic acid carboxymethylamide or 2-(2'-hydroxy 5phenylphenyD-benztriazole 5 sulphonic acid carboxymethylamiderespectively is obtained.

EXAMPLE 12 The still moist az/o dyestuif (obtained by coupling 13.8parts of diazotised o-nitraniline with 21.4 parts of4-hydroxy-4'-carboxydiphenyl), is dissolved with 20 parts of sodiumhydroxide in 200 parts by volume of water. The solution is then reducedat 4050 until decolouration occurs by the addition of zinc dust and theWhole is stirred for 12 hours at room temperature. The reaction mixtureis acidified with excess hydrochloric acid, the precipitate is filteredoff under suction and crystallised from a mix ture ofdimethylformamide/glacial acetic acid 2-[2'-hydroxy-S (4-carboxyphenyl-phenyl] -benztriazole which melts above 280 is obtained.

EXAMPLE 13 27.9 parts of2-(2-hydroxy-3'-,8-methylallyl-5'-methylphenyl)-benztriazole (M.P. 94,obtained by Claisen rearrangement of the ether obtained from2-(2-hydroxy- 5'-methylphenyl)-benztriazole and methallyl chloride), 12parts by volume of an aqueous solution of thioglycolic acid and 0.2 partof benzoyl peroxide in 200 parts by volume of glacial acetic acid arerefluxed for 12 hours. The acetic acid solution is diluted, while stillhot, with water, the precipitate formed is filtered off under suctionand dissolved in 2 N sodium hydroxide solution. The yellow, alkalinesolution is filtered and acidified with 2 N hydrochloric acid. Theprecipitate formed is filtered off under suction, washed with water andcrystallised from ligroin. 2(2-hydroxy-3'-B-methyl-'y-carboxymethylrnercapto-propyl-S-methylphenyl)-benztriazolewhich melts at 114 is obtained.

If in the above example, instead of 12 parts by volume of an 80%solution of thioglycolic acid, 12 parts of ,8- thiopropionic acid areused and the procedure given above is followed, then2-(2'-hydroxy-3-fl-methyl-' -carboxyethylmercaptopropyl-5methylphenyl)benztriazole is obtained. M.P. 142. Esterification of the two acids withethanol, butanol or octanol yields the following compounds:

2- (2'-hydroxy-3 '-methyl-;3-methyl' carbethoxymethylmercapto -propyl-5'-methylphenyl) -benztriazole 2- (2'-hydroxy-3 '-{3-methyl-y-(carbobutoxymethylmercapto -propyl-5 -methylphenyl -benztriazole 2-(2'-hydroxy-3 -,3-methyl-' (carbooctyloxymethylmercapto-propyl-5-methylphenyl) -benztriazole 2- [2-hydroxy-3 '-,B-methyl-'y-(18'-carbethoxyethylmercapto -propyl-5 '-methylphenyl] -b enztriazole 2-[2-hydroxy-3 '-/3-methyl-'y- (fi'-carbobutoxyethylmercap topropyl-S'-methylphenyl] -b enztriazole 2- [2'-hydroxy-38-methyl-yfl-carbooctyloxyethylmercapto -propyl-5 -methylphenyl]-benztriazole 2- [2'-hydroxy-3 '--y- ,3'-cyclohexyloxycarbonyl-ethylmercapto )-propyl-5 '-methylphenyl] -benzotriazole.

EXAMPLE 14 The solution of the fi-[3'-benztriazolyl-(2")-4-hydroxyphenyl-(1')]-propionic acid chloride as obtained accordingto Example 5 is heated with excess benzyl alcohol for three hours on aboiling water bath. The excess benzyl alcohol and the dimethyl formamideis removed in vacuo. The 2-(2'-hydroxy-5 ,8 carbobenzyloxyethylphenyl)-benztriazole so obtained is recrystallised from isopropanol and melts at117.

Analogously 2- 2-hydroxy-5 -}8-carbomethyloxyethylphenyl benztriazole 2-2-hydroxy-5 -B-carboallyloxyethylphenyl benztriazole 2-2'-hydroxy-5'-B-carbophenyloxyethylphenyl benztriazole.

EXAMPLE 15 15 parts of2-(2'-hydroxy-3'-methyl-5'-B-carboxyethylphenyl)--chlorobenztriazole, 30parts of dodecyl alcohol and 0.8 part of sulphuric acid are refluxed forthree hours at 12 mm. pressure. At the same pressure, the excess alcoholis distilled off and the residue of the distillation is poured ontocrushed ice. The 2-(2'-hydroxy-3-methyl-5- pcarbododecyloxyethylphenyl)-5-chlorobenztriazole so obtained isrecrystallised from isopropanol and melts at 82.

The following are prepared analogously:

2- (2'-hydr0xy-5'-,8 -{/9'- [B"- (ethoxycarbonyl-ethylmercapto]-ethoxycarbonyl}-ethyl-phenyl)-benzotriazole,

2- 2'-hydroxy-3'-methyl-5 -;3-carbododecyloxyethylphenyl-5-methylbenztriazole,

2-(2'-hydroxy-3-methyl-5'-;8-carbododecyloxyethylphenyl)-4,6-dichlorobenztriazole2-(2-hydroxy-3'-methyl-5-;8-carbododecyloxyethylphenyl -5,6-dimethylbenztriazole,

2-(2-hydroxy-3-methyl5'- 3-carbododecyloxyethylphenyl)-5-methoxybenztriazole,

2-(2-hydroxy-3methyl-5'- 8-carbododecyloxyethyl phenyl)-5-ethoxybenztriazole.

EXAMPLE 16 parts of 2-(2'-hydroxy-3'-o-carboxyphenylmethyl-5-methylphenyl)-benztriazole are refluxed for six hours with 30 parts ofbutanol and 1 part of sulphuric acid. The resultant solution is pouredonto parts of ice 400 parts of water. The 2-(2'-hydroxy-3 ocarbobutoxyphenylmethyl 5 methylphenyl)-benztriazole crystallises uponstirring, is collected by filtration and recrystallised from ethanol.'It melts at 73.

The following esters are prepared in an analogous manner:

2- (2-hydroxy-3-o-carbobutoxyphenylmethyl-S '-chlorophenyl-benztria2ole,

2- 2-hyroxy-3-o-carbobutoxyphenylmethyl-5'-chlorophenyl)-5-chlorobenztriazole,

2- (2-hydroxy-3- [o-carbo-B- fl'-carboethoxy-ethylmercapto)-ethoxyphenylmethyl] -5 '-methylphenyl benzotriazole,

2- 2'-hydroxy-3'-'y-carbobutoxybutyl-5 '-methylphenyl) benztriazole,

2- 2'-hydroxy-5 '-carbobutoxymethylphenyl) benztriazole.

EXAMPLE 17 2-(2'-hydroxy-5'-p-carboxyphenylphenyl) benztriazole istransformed into its acid chloride according to Example 5. The solutionin dimethylformamide so obtained is reacted with excess allyl alcoholanalogously to Example 14. The resultant 2-(2-hydroxy-5' pcarboallyloxyphenylphenyl)-benztriazole is worked up as in Example 14and is thereupon recrystallised from ethanol. It melts at 138.

EXAMPLE 18 24.1 parts of2-(2'-hydroxy-3'-methyl-5-13-carboxyethylphenyl)-benztriazole-S-carboxylicacid are suspended in 1 part of dimethylformamide and 100 parts ofchlorobenzene. 28 parts of thionyl chloride are added thereto with goodstirring. The mixture is slowly heated to reflux temperature and is keptat this temperature until a clear solution is obtained. After anadditional quarter of an hour at reflux temperature, 50 parts ofchlorobenzene are distilled off whereby some excess thionyl chloride isdriven off also. The remaining solution is cooled to 70 whereupon partsof ethanol are added. The resultant mixture is refluxed for 45 minutes.Cooling to 0, a crystalline product is obtained which is filtered off.Further amounts can be obtained by concentrating the mother liquors. The2-(2-hydroxy-3'-methyl-5'-,B-carboethoxyethylphenyl)-S-carboethoxybenztriazoleso obtained is recrystallised from ethanol and melts at 104.

Reaction with the corresponding alcohols yields the following compounds:

2- 2-hydroxy-3'-methyl-5'-fi-carbomethoxyethylphenyl S-carbomethoxybenztriazole 2- 2-hydroxy-3'-methyl-5'-fi'-carbobutoxyethylphenyl -5 carbobutoxybenztriazole 2-2-hydroxy-3'-methyl-5'-fi-carbooctyloxyethylphenyl 5-carbooctyloxybenztriazole 2- (2'-hydroxy-3 -rnethyl-5'-B-carbocyclohexyloxyethylphenyl -5carbocyclohexyloxybenztriazole 2-(2-hydroxy-3-methyl-5 8-carbobenzyloxyethylphenylS-carbobenzyloxybenztriazole 2- 2-hydroxy-3-methyl-5'-fl-carbophenoxyethylphenyl 5 -carbophenoxybenztriazole.

EXAMPLE 19 34.1 parts of 2(2-hydroxy-3'-methyl-5'-;3-carboxyethylphenyl)-benztriazole 5 carboxylicacid are transformed into the acid chloride according to Example 18. Thesolution so obtained is diluted with 100 parts by volume of ligroinwhile still warm. Thereupon 16 parts of methylamine (in form of a 30%aqoeous solution) are added and the mixture is stirred for 30 minutes atreflux. After cooling the mixture is acidified with 20 parts by volumeof concentrated hydrochloric acid. The 2-(2'-hydroxy-3'-methyl 5'fl-carbomethylamidoethylphenyl)- benztriazole-S-carbonic acidmethylamide precipitated is recrystallised from dimethylformamide. Itmelts above 260.

The following derivatives are prepared analogously 2-(2-hydroxy--methyl-5- 3-carbocyclohexylamidoethylphenyl)benztriazole-S-earbonicacid cyclohexylamide2-(2-hydroxy-3-methyl-5'-5-carbobenzylamidoethylphenyl)benztriazole-S-carbonicacid benzylamide.

EXAMPLE 20 34.1 parts of2-(2-hydroxy-3'-methyl-5'-,3-carboxyethylphenyl)-benztriazole-5-carboxylicacid are transformed into the acid chloride according to Example 18. Thesolution so obtained is chilled while being stirred. The acid chloridecrystallises and is filtered off and washed with ligroin. It isdissolved in 100 parts by volume of methylethylketone to which solution45 parts of morpholine are added with good stirring. To the thickreaction mixture are added 500 parts of water and 30 parts by volume ofconcentrated hydrochloric acid. The oil remaining is dissolved inethanol. Upon dilution with Water the 2-(2-hydroxy- 3-methyl 5fi-carbomorpholido-ethylphenyl)-benztriazole-S-carbonic acid morpholinecrystallises.

The following products are obtained in an analogous manner:2-(2-hydroxy-'-methyl-5'-}8-carbodimethylamidoethylphenyl)-benztriazole-5-carbonicacid dimethylamide 2-(2'-hydroxy-'-methyl-5'-fl-carbobutylamidoethylphenyl)-benztriazole-5-carbonic acidbutylamide.

EXAMPLE 21 100 parts of polyethylene powder (DFD 4400, of Union CarbideInternational Chemical Company, 30 E. 42nd St., New York, N.Y., USA.)are mixed with 0.25 part of one of the compounds given below and themixture is extruded into a foil of about 0.06 mm. thickness. Cuttings 17 from this film, which absorbs UV light, were exposed for 250 hours ina fadeometer. The content of actinic agent in the film was determinedbefore and after exposure spectrophotometrically. The losses sodetermined are given in Table 1.

TA B LE 1 Loss after 250 hrs. in fadeometer, N0. Compound percentComparative compounds without carboxylic acid derivative group:

1 2-(2 -l1y droxy-5 -methylpheny1) -benztriazle 72 22-(2-hydroxy-5-tert-butylphenyl)-benztriazole 50 32-(2'-hydroxy-5-chlor0phenyl) -benztriazo1e 50 4-2-(2-hydrcity-3-tert.butyl-5-methylpheny1) 33 benztriazole. 52-(2-hydr0xy-5-n1ethylpheny1)-5-ehloro 40 benztriazole.

Compounds according to the invention:

6 2-(2-hydroxy-5- 3carbodecyloxyethylphenyl) 9 benztriazole. 7 2-221-113iiroxy-5-fl-carbobutoxyethylphenyl) -benz- 12 T1820 e. 82-(2-hydroxy-5'-B-carbo-x-ethylhexyloxyethyl- 8 phenyD-benztriazole. 92(2-hydroxy-5-B-carbocyclohexyloxyethylphenyl)- 10 benztriazole. 102-(2-hydroxy-3-Bearb obutoxyphenylmethyl-5- 9methylphenyl)-benztriazole.

As can be seen from Table I, a much smaller loss on exposure occurs withthe compounds of the present invention than with the previously known UVabsorbers. This difference is probably due. to the better fastness tosublimation of the actinic agents according to the invention comparedwith that of the comparative substances. If a foil containing thecompound 1 in Table I is placed between two quartz plates which areputtied together and exposed in the same way, as above, then under theseconditions only a loss of 10% occurs. This improvement in the stabilityto sublimation is clearly seen in spinning polypropylene fibres. Whencompound 1 of the table is used, then a sublimation occurs which becomesapparent by the formation of crystal beads on the cold parts of thespinning machine, but when the compound of Example 3 is used, no suchnuisance can be observed.

EXAMPLE 22 Cellulose acetate films were produced by drawing onto glass asolution consisting of 150 parts of acetyl cellulose (2- /2 Acetate, ofLonza A.G. Weil, Germany), parts of dibutyl phthalate, 825 parts ofacetone and 0.5 part of the compound 2-(2-hydroxy-3,5'dimethylphenyl)-S-[B-carboethoxyethylmercapto benztriazole. Cuttingsfrom these films were exposed for 1000 hours in a fadeometer and thelight absorbed at 365 m was measured before and after exposure.Transmission before exposure was 10% and after exposure 12%. The loss ofcontent of UV absorber occurring on exposure was only 9%. The film soexposed showed no signs of brittleness which occur with films of thesame composition but not containing actinic agent.

Light fast, UV-absorbing films can be produced in an analogous mannerfrom other cellulose esters which are soluble in acetone.

EXAMPLE 23 N 01130 0 o-oso N no on,

and 1 part of benzoyl peroxide and the mixture is then cured between twoglass plates at 80. The resulting 2 mm. thick polyester resin plateformed absorbs substantially all UV light of wave lengths under 360 mand shows an improved resistance to yellowing. Upon 500 hours exposurein the fadeometer its loss in transmission at 420 m (which loss is ameasure of the yellowing) is 3%, Whereas a plate produced in the sameway but without the addition of said light stabiliser shows a loss of15% under the same conditions.

EXAMPLE 24 EXAMPLE 25 100 parts of methylmethacrylate and 0.1 part of2-(2- 25 hydroxy-5 p carbobutoxyethylphenyl)-benztriazole together with0.2 part of lauroyl peroxide as polymerisation accelerator are mixed andpolymerised at 70 in a glass mould into a plate of 4 mm. thickness. Theplate was exposed for 1000 hours in a fadeometer and the trans missionmeasured at 360 m it was less than l%no different from that beforeexposure. The plate had neither a yellow colouring nor surface cracks.This material can, therefore, be used as light stable UV filter.

EXAMPLE 26 250 parts of powdery polypropylene free of antioxidant(Pro-Fax 6501 of Hercules Powder Co.) are intimately mixed with one partof N H3O HO CH CHICHJCH COOCHgCHgSCHzCHg-COOCzHQ 4.5

2-{2 hydroxy 3 6 [carbo-[i-(fi"-carbethoxy-ethylmercapto) ethoxy] butyl5' methylphenyl}5,6-dimethyl-benztriazole stabilizer. The mixture iscalendered on a set of mixing rollers for 7 minutes at 175 C. Yielding ahomogeneous sheet which is drawn from the rollers and cooled on a smoothsurface. parts of this sheeted material are moulded in'a littlehydraulic press at 200 to form a film of 0.6 mm. thickness. From thisbands of 5 mm. width are cut and weathered under natural conditions andtested periodically with respect to their brittleness by manual bending.The aforementioned material forms cracks upon bending after two monthsweathering while similar bands prepared without the addition of astabiliser crack already after one months weathering under the sameconditions.

We claim:

1. A compound of the formula 4 N HO x)..-1-Y-w] l L m l A N 6\/\ 1 themolecular weight of which compound does not exceed 600, and in theformula of which X is a member selected from the group consisting of-o-, -s-, -so.o-, -ooo-, SOn-, SO1Nand-CON- lower alkyl lower alkylwherein said X is bound only by one of the oxygen, carbon and sulfuratoms contained in said X to at most one of the nuclei A and B,

Y is a member selected from the group consisting of alkylene with 1 to 4carbon atoms, lower alkyl-S- lower alkyl having a total of from 4 to 6carbon atoms, and

W is a member selected from the group consisting of COO.alkyl whereinthe alkyl moiety is alkyl of 4 to 18 carbon atoms, COO.cyc1oalkylwherein the cycloalkyl wherein the cycloalkyl moiety is cycloalkyl of 4to 12 carbon atoms and --COO-benzyl,

m and n are each independently of the other, one of the integers 1 and2,

the first {(X) YW] grouping being linked in one of the positions 5 atring A, or 3', 4 or 5 at ring B, and a second grouping {-(X),, -YW] ifpresent, being linked to one of the aforesaid positions at that ring, ofrings A and B, which is free from said first grouping,

nucleus A is substituted in at least one of the 4-, 5- and 6-p0sitionswhich is free from said grouping by at least one member selected fromthe group consisting of hydrogen, lower alkyl, lower alkoxy,alkoxy-carbonyl of from 2 to 19 carbon atoms, cyclohexyloxycarbonyl,benzyloxycarbonyl, phenoxycarbonyl, N (mono higher alkyl) carbamyl andN- (mono-higher alkyl)-sulfamyl, higher alkyl in the last two membershaving from 4 to 18 carbon atoms, N,N-di-alkyl-carbamyl,N,N-di-alkyl-sulfamyl, the total number of carbon atoms in both alkylsubstituents of each of the two last-mentioned members not exceeding 20,N-cyclohexyl-sulfamyl, N-benzylsulfamyl, N-lower alkoxy-loweralkyl-sulfamyl, N-hydroxy-lower alkylsulfamyl, lower alkyl-sulfonyl andhalogen,

and the nucleus B is substituted in at least one of the 3'-, 4'- and5-positions, not substituted by said grouping iE(X),, -Y--W], by amember selected from the group consisting of hydrogen, lower alkyl,cycloalkyl of from 5 to 6 ring carbon atoms, chlorine, benzyl or phenyl.

2. A compound as defined in claim 1 which is of the formula N HO 20 3. Acompound as defined in claim 1 which is of the formula /N\ H0 on? MG 0 0crncrncrnon,

4. A compound as defined in claim 1 which is of the formula N HO 5. Acompound as defined in claim 1 which is of the formula 6. A compound asdefined in claim 1 which is of the formula H O CH:

7. A compound as defined in claim 1 which is of the 3,214,436 10/1965Boyle et al.

r ALTON D. ROLLINS, Primary Examiner 0

